Compositions stabilized with dioxaphosphepines

ABSTRACT

Compounds of the formula I    &lt;IMAGE&gt;  (I)  wherein R1 is C1-C18 alkyl, R2 is hydrogen or C1-C18 alkyl, and A is a substituted primary or secondary aliphatic or alicyclic, aromatic or araliphatic amine, in which the substituents are identical or different, a heterocyclic amine or a hydrazine derivative.

This is a continuation of application Ser. No. 184,876, filed on Sept.8, 1980, now abandoned, which in turn is a divisional of applicationSer. No. 39,701 filed on May 18, 1979, now U.S. Pat. No. 4,259,492,issued Mar. 31, 1981.

The present invention relates to new N-substituted6-amino-dibenz[d,f][1,3,2]dioxaphosphepines, to the production thereof,to their use as stabilisers for organic material, and to the organicmaterial stabilised by means of these compounds.

Phosphonites are known to be stabilisers. These phosphonites do nothowever meet in every respect the high requirements that a stabiliserhas to meet, particularly in respect of storage stability, waterabsorption, sensitivity to hydrolysis, processing stabilisation, colourbehaviour, volatility, migration behaviour, compatibility and improvedstability to light.

It was the object of the invention to provide stabilisers which do nothave these disadvantages, or have them to a lesser extent.

The present invention relates to N-substituted6-amino-dibenz[d,f][1,3,2]dioxaphosphepines of the formula (I) ##STR2##wherein R₁ is C₁ -C₁₈ alkyl,

R₂ is hydrogen or C₁ -C₁₈ alkyl, and

A is a substituted primary or secondary aliphatic or alicyclic, aromaticor araliphatic amine, in which the substituents are identical ordifferent, a heterocyclic amine or a hydrazine derivative.

As C₁ -C₁₈ alkyl, R₁ and R₂ are in particular straight-chain orbranched-chain alkyl having 1-8 C atoms, for example methyl, ethyl,n-propyl, iso-propyl, sec-butyl, tert-butyl, tert-pentyl, n-octyl,2-ethylhexyl or 1,1,3,3-tetramethylbutyl. R₁ is preferably α-branched.In particularly preferred compounds, R₁ and R₂ have the same meaning.

The radicals R₂ are preferably in the 1- and 11-position, but especiallyin the 2- and 10-position. ##STR3##

A is a substituted primary or secondary amine in which the substituentsare identical or different, which amine can contain up to six primaryand/or secondary amino groups. Preferred compounds are those in whichall primary or secondary amine nitrogen atoms occurring in the moleculeare substituted by a group of the formula II ##STR4##

The symbols R₁ and R₂ in the formula II have the meanings given above.

Of interest in particular are secondary amines, and especiallybranched-chain amines.

Preferred amines A are therefore those of the formula III ##STR5##wherein R₃ is hydrogen, C₁ -C₂₂ alkyl, C₂ -C₂₁ oxa- or thiaalkyl, C₃-C₁₈ alkenyl, C₃ -C₁₈ alkynyl, C₂ -C₆ hydroxyalkyl, C₃ -C₂₄alkoxycarbonylalkyl, C₅ -C₁₂ cycloalkyl, C₆ -C₁₄ aryl, C₇ -C₁₅ alkaryl,C₇ -C₁₅ aralkyl, a substituted or unsubstituted C₅ -C₁₇ piperidin-4-ylgroup, or a group of the formula II in which R₁ and R₂ have the meaningsgiven above, and

R₄ is C₁ -C₂₂ alkyl, C₂ -C₂₁ oxa- or thiaalkyl, C₃ -C₁₈ alkenyl, C₃ -C₁₈alkynyl, C₂ -C₆ hydroxyalkyl, C₃ -C₂₄ alkoxycarbonylalkyl, C₅ -C₁₂cycloalkyl, C₆ -C₁₄ aryl, C₇ -C₁₅ aralkyl, a substituted orunsubstituted C₅ -C₁₇ piperidin-4-yl group, a group of the formula IV##STR6## wherein R₃ has the meaning given above,

n is 0 or 1,

R₅ is C₂ -C₂₂ alkylene, C₄ -C₂₂ alkenylene, C₄ -C₂₂ alkynylene or C₅ -C₉cycloalkylene, each of which can be interrupted with one or two oxygenor sulfur atoms, or R₅ is a group of the formula VI ##STR7## in which R₆is --O--, --S-- or --(R₇)C(R₈)--, wherein R₇ and R₈ independently of oneanother are hydrogen or C₁ -C₈ alkyl, or R₇ and R₈ together with the Catom to which they are attached form C₅ -C₁₂ cycloalkyl, or R₇ and R₈together are 1,4-cyclohexylenedimethylene or1,3,3-trimethylcyclohexylene-1,5, or R₅ is also phenylene, biphenyleneor a group of the formula ##STR8## wherein R₆ has the meaning givenabove, and r, t and n independently of one another are 2, 3, 4, 5 or 6,

m is 0, 1, 2 or 3,

Q is a group of the formula II, wherein R₁ and R₂ have the meaningsgiven above, or

R₃ and R₄ together with the N atom to which they are attached are alsosubstituted pyrrolidine, oxazolidine, piperidine or morpholine, or R₃and R₄ together form the radical --CH₂ --CH₂ --N(Q)--CH₂ --CH₂ --wherein Q has the meaning given above.

If R₃ and R₄ are each C₁ -C₂₂ alkyl, they can be methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl,isohexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n-nonyl, decyl, dodecyl,tetradecyl, hexadecyl, octadecyl, eicosyl or docosyl. As alkyl groups,R₃ and R₄ preferably contain 1-18 C atoms, with R₃ containing inparticular 1-12 C atoms and R₄ in particular 1-4 C atoms. As C₂ -C₂₁,especially C₄ -C₂₁, oxa- or thiaalkyl, R₃ and R₄ are preferably alkoxy-or alkylthiopropyl, such as butoxypropyl, dodecylthiopropyl,octyloxypropyl or octadecyloxypropyl.

As C₃ -C₁₈ alkenyl, R₃ and R₄ are for example allyl, methallyl,n-hex-3-enyl, n-oct-4-enyl or n-undec-10-enyl. Allyl and methallyl arepreferred, and especially allyl.

As C₃ -C₁₈ alkynyl, R₃ and R₄ are for example propargyl, n-butyl-1-ynyl,n-but-2-ynyl or n-hex-1-ynyl. Alkynyl groups having 3 or 4 C atoms andparticularly propargyl are preferred.

If R₃ and R₄ are each hydroxyalkyl having 1-6 C atoms, they can be2-hydroxypropyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl or6-hydroxyhexyl.

If R₃ and R₄ are each C₃ -C₂₄ alkoxycarbonylalkyl, preferably C₃ -C₂₄alkoxycarbonylmethyl or -ethyl and in particular C₃ -C₁₄alkoxycarbonylmethyl or C₃ -C₁₅ alkoxycarbonylethyl, they can be forexample methoxycarbonylmethyl, ethoxymethyl, methoxycarbonylethyl,octoxycarbonylmethyl, octoxycarbonylbutyl, dodecyloxycarbonylethyl oroctadecyloxycarbonylethyl.

As C₅ -C₁₂, preferably C₅ -C₈ and especially C₆, cycloalkyl, R₃ and R₄are for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl or cyclododecyl.

As C₆ -C₁₄ aryl, R₃ and R₄ are for example phenyl, α-naphthyl,β-naphthyl or phenanthryl. Phenyl groups are preferred.

If R₃ and R₄ are aralkyl having C₇ -C₁₅ C atoms, they are for examplebenzyl, α-phenylethyl, α,α-dimethylbenzyl or 2-phenylethyl, preferablybenzyl.

As C₇ -C₁₅ alkaryl groups, R₃ and R₄ can be for example tolyl,2,6-dimethylphenyl, 2,6-diethylphenyl, 2,4,6-triisopropylphenyl or4-tert-butylphenyl.

If R₃ and R₄ are C₅ -C₁₇ piperidin-4-yl groups, they can be for exampleunsubstituted piperidin-4-yl, or the piperidine can be substituted by upto 5 alkyl groups, preferably by methyl or ethyl groups. Preferredsubstitution positions are the 2- and 6-positions in the piperidinering. They can also be 3,3,5-trimethyl-8-ethoxy-bicyclo[4,4,0]dec-2-yl.

R₃ and R₄ can therefore form piperidin-4-yl groups of the followingstructure: ##STR9## wherein R₉ is hydrogen or methyl, and R₁₀ ishydrogen, oxyl, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl, C₃ -C₆ alkynyl, C₇ -C₁₂aralkyl, C₂ -C₂₁ alkoxyalkyl, an aliphatic acyl group having 1-4 Catoms, or a group --CH₂ COOR₁₁ wherein R₁₁ is C₁ -C₁₂ alkyl, C₃ -C₈alkenyl, phenyl, C₇ -C₈ aralkyl or cyclohexyl.

Very particularly preferred piperidin-4-yl groups are those wherein R₉is hydrogen, and R₁₀ is hydrogen, methyl or acetyl.

The preferred meaning of R₉ is hydrogen.

As C₁ -C₁₈ alkyl, R₁₀ is for example methyl, ethyl, n-propyl, n-butyl,n-pentyl, n-octyl, n-decyl, n-dodecyl or actadecyl. Preferred alkylgroups are those having 1 to 12 C atoms, especially those having 1 to 8C atoms, in particular those having 1 to 4 C atoms, and above allmethyl.

As C₃ -C₈ alkenyl, R₁₀ is for example allyl, 3-methyl-2-butenyl,2-butenyl, 2-hexenyl or 2-octenyl, especially allyl.

As C₃ -C₆ alkynyl, R₁₀ is for example propargyl.

As C₇ -C₁₂ aralkyl, R₁₀ is for example benzyl, β-phenylethyl or4-tert-butyl-benzyl, preferably benzyl.

If R₁₀ is C₂ -C₂₁ alkoxyalkyl, the alkyl moiety can contain 1 to 3 Catoms, and the alkoxy moiety can consist of 1 to 18 C atoms, such as inmethoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl,2-n-butoxyethyl, 3-n-butoxypropyl, 2-octoxyethyl or 2-octadecyloxyethyl.To be particularly mentioned are compounds in which R₁₀ is analkoxyalkyl group having 2 to 6 C atoms.

As an aliphatic acyl group having 1 to 4 C atoms, R₁₀ is for exampleformyl, acetyl, acryloyl or crotonyl, especially acetyl.

If R₁₀ is the group --CH₂ COOR₁₁, R₁₁ as C₁ -C₁₂ alkyl is for examplemethyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, isopentyl,n-octyl or n-dodecyl. Preferably R₁₁ is C₁ -C₄ alkyl. As C₃ -C₈ alkenyl,R₁₁ is for example allyl, 2-butenyl or 2-hexenyl. As C₇ -C₈ aralkyl, R₁₁is for example benzyl or α-phenylethyl.

If R₃ is a group of the formula II, this group preferably has the samesubstitution as the dibenz[d,f][1,3,2]dioxaphosphepin-6-yl group alreadypresent in the molecule.

If R₃ and R₄ with the N atom to which they are attached form apyrrolidine, oxazolidine, piperidine or morpholine ring, theseheterocycles can be substituted by up to five methyl or ethyl groups.These ring systems are preferably unsubstituted.

The symbol n can be 0 or preferably 1.

As C₂ -C₂₂ alkylene, preferably C₂ -C₉ and particularly C₂ -C₆ alkylene,R₅ can be for example dimethylene, trimethylene, tetramethylene,hexamethylene, octamethylene, nonamethylene,2,2,4-trimethylhexamethylene, decamethylene, dodecamethylene,octadecamethyl or docosamethylene, If the alkylene groups areinterrupted by --O-- or --S--, they can be 2-thiapropylene-1,3,3-thiapentylene-1,5,4-oxaheptamethylene or 3,6-dioxaoctylene-1,8.

If R₅ is C₄ -C₂₂ alkenylene or alkynylene, it is for example2-butenylene-1,4, 2-butynylene-1,4, 2,4-hexadiinylene-1, orpropenylene-1,3.

As C₅ -C₉ cycloalkylene, R₅ is for example 1,2-cyclopentylene,1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene,1,4-cycloheptylene or 1,2-cyclononylene. As cycloalkylene, R₅ preferablyhas 6 C atoms.

R₇ and R₈ as C₁ -C₈ alkyl are for example ethyl, n-propyl, isopropyl,n-butyl, n-phenyl, n-hexyl or n-octyl. As alkyl groups, R₇ and R₈ arepreferably however methyl.

With C atom to which they are attached, R₇ and R₈ can also form C₅ -C₁₂cycloalkyl, preferably cyclohexyl. It can be cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl or cyclododecyl.

Independently of one another, r, t and n are 2, 3, 4, 5 or 6; they arepreferably however identical, and are in particular 2 or 3.

m can be 0, 1, 2 or 3. Preferably m is 0 or 1, but particularly 0.

If radicals Q are present in the compounds, these are preferablysubstituted in the same way as the otherdibenz[d,f][1,3,2]dioxaphosphepin-6-yl groups present in the molecule.

Preferred compounds of the formula I are those wherein

R₁ and R₂ are each C₁ -C₈ alkyl,

A is a group --N(R₃)R₄ (III), wherein

R₃ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, C₃ -C₂₄alkoxycarbonylmethyl or -ethyl, C₅ -C₁₂ cycloalkyl, phenyl, benzyl, C₇-C₁₅ alkaryl, a substituted or unsubstituted C₅ -C₁₇ piperidin-4-ylgroup, or a group of the formula II, wherein R₁ and R₂ have the meaningsgiven above,

R₄ is C₁ -C₁₈ alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, C₃ -C₂₄alkoxycarbonylmethyl or -ethyl, C₅ -C₁₂ cycloalkyl, phenyl, benzyl, C₇-C₁₅ alkaryl, a substituted or unsubstituted C₅ -C₁₇ piperidin-4-ylgroup, a group of the formula IV or V, wherein R₃ has the meaning givenabove,

n is 0 or 1,

R₅ is C₂ -C₉ alkylene which can be interrupted with one or two oxygen orsulfur atoms, or it is cyclohexylene, or a group of the formula VI,wherein

R₆ is --O--, --S-- or --(R₇)C(R₈)--, wherein

R₇ and R₈ independently of one another are hydrogen or methyl, or

R₇ and R₈ together with the C atom to which they are attached formcyclohexylene, or

R₇ and R₈ together are 1,4-cyclohexylenedimethylene or1,3,3-trimethyl-cyclohexylene-1,5,

r, t and n are 2 or 3,

m is 0 or 1,

Q is a group of the formula II, wherein R₁ and R₂ have the meaningsgiven above, or

R₃ and R₄ together with the N atom to which they are attached form apyrrolidine, oxozolidine, piperidine or morpholine ring, or

R₃ and R₄ together are the radical --CH₂ CH₂ --N(Q)--CH₂ CH₂ --, whereinQ has the meaning given above.

Of interest are compounds of the formula I wherein

R₁ is α-branched C₃ -C₈ alkyl,

R₂ is C₁ -C₈ alkyl,

A is a group --N(R₃)R₄ (III), wherein

R₃ is hydrogen, C₁ -C₁₈ alkyl, allyl, propargyl, C₃ -C₁₄alkoxycarbonylmethyl, C₃ -C₁₅ alkoxycarbonylethyl or C₅ -C₈ cycloalkyl,

R₄ is C₁ -C₄ alkyl, allyl, propargyl, C₃ -C₁₄ alkoxycarbonylmethyl, C₃-C₁₅ alkoxycarbonylethyl, C₅ -C₈ cycloalkyl, or a group of the formulaIV or V, wherein R₃ has the meaning given above,

n is 1,

R₅ is C₂ -C₆ alkylene,

r, t and n are 2 or 3,

m is 0,

Q is a group of the formula II, wherein R₁ and R₂ have the meaningsgiven above, or

R₃ and R₄ together with the C atom to which they are attached form apiperidine or morpholine ring, or

R₃ and R₄ together are the radical --CH₂ CH₂ --N(Q)--CH₂ CH₂ -- whereinQ has the meaning given above.

Particularly preferred are compounds of the formula I wherein

R₁ and R₂ are α-branched C₃ -C₈ alkyl,

A is a group --N(R₃)R₄ (III), wherein

R₃ is hydrogen, C₁ -C₁₂ alkyl or cyclohexyl,

R₄ is C₁ -C₄ alkyl, cyclohexyl, or a group of the formula IV, wherein R₃has the meaning given above, and Q is a group of the formula II, whereinR₁ and R₂ have the meanings given above,

n is 1,

R₅ is C₂ -C₆ alkylene, or

R₃ and R₄ together with the C atom to which they are attached form apiperidine or morpholine ring, or

R₃ and R₄ together are the radical --CH₂ CH₂ --N(Q)--CH₂ CH₂ --, whereinQ has the meaning given above.

Examples of compounds of the formula I are:

(1)6-(N,N-di-n-octylamino)-2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphephine,

(2)6-(2'-aza-3',3',5'-trimethyl-8'-ethoxy-bicyclo[4.4.0]dec-2'-yl-2,4,8,10-tetra-tert-octyl-dibenz[d,f][1,3,2]dioxaphosphepine,

(3)6-(N-2',6'-dimethylphenyl-N-cyclohexylamino)-2,10-dimethyl-4,8-di-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepine,

(4)6-(N-cyclododecyl-N-tert-octylamino)-2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphephine,

(5)6-(N-tert-butylamino)-2,4,8,10-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepine,

(6)6-(N-n-octadecylamino)-2,10-dimethyl-4,8-di-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepine,

(7)6-(N-cyclododecylamino)-2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepine,

(8)6-(N-2',6'-dimethylphenylamino)-2,10-dimethyl-4,8-di-tert-octyl-dibenz[d,f][1,3,2]dioxaphosphepine,

(9)6-(N-p-tert-octylphenyl-N-isopropylamino)-2,4,8,10-tetra-tert-pentyl-dibenz[d,f][1,3,2]dioxaphosphepine,

(10)6-(N-cyclohexyl-N-allylamino)-2,4,8,10-tetra-tert-octyl-dibenz[d,f][1,3,2]dioxaphosphepine,

(11)2,2-bis-[4'-[N-2",4",8",10"-tetra-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6"-yl)-amino]-cyclohexyl]-propane,

(12)N,N'-bis-(2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphetin-6-yl)-benzidine,

(13)N,N'-bis-(2,4,8,10-tetra-tert-pentyl-dibenz[d,f][1,3,2]dioxaphosphetin-6-yl)-N,N'-dicyclopentylhexamethylene-diamine,

(14)N,N'-bis-(2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphetin-6-yl)-N,N'-di-isopropylhydrazine,

(15)N,N'-bis-(2,10-di-tert-octyl-4,8-di-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphetin-6-yl)-N,N'-(1'-isopropyl-2'-methylpropyl)-ethylenediamine,

(16)N,N'-bis-(2',4',8',10'-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6'-yl)-4,9-dioxadodecamethylenediamine,

(17)N,N'-bis-(2,10-dimethyl-4,8-di-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6-yl)-N,N'-dicycloheptylhexamethylenediamine.

(18)1,4-bis-(2',4',8',10'-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6'-yl)-2,5-dimethylpiperazine,

(19)1,4-bis-[N-(2',4',8',10'-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphin-6'-yl)-aminopropyl]-piperazine,

(20)N,N',N"-tris-(2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6'-yl)-diethylenetriamine,

(21)N,N-bis[3-[N'-(2',4',8',10'-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6'-yl)]-aminopropyl]-N-(2",4",8",10"-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6"-yl)-amine,

(22)N,N-bis-(2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6-yl)-N-n-butylamine,

(23)N,N'-bis-(2,4,8,10-tetra-tert-pentyl-dibenz[d,f][1,3,2]dioxaphosphepin-6-yl)-N,N'-diisopropylhydrazine,

(24)N-cyclohexyl-N-(2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6-yl)-aminosuccinicacid-dioctyl ester,

(25) R--N--(cyclohexyl)--(CH₂)₃ --N(R)--(CH₂)₃ --N(R)--(CH₂)₃--N(R)--(CH₂)₃ --N(cyclohexyl)--R, and

(26) R--N(H)--[CH₂ --CH₂ --N(R)]₄ --CH₂ CH₂ --N(H)R.

In the formulae 25 and 26, R denotes the group(2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6-yl):##STR10##

The phosphonites of the formula I can be produced by methods known perse, particularly by amidation or transamidation reactions, for exampleby reacting a phosphonite of the formula VII ##STR11## wherein X is areactive group, and R₁ and R₂ have the meanings given above, with anamine ZA, particularly with an amine of the formula VIII ##STR12##wherein Z is hydrogen or an Na, Li or K atom, and R₃ and R₄ have themeanings given above.

A reactive group X is for example halogen, particularly chlorine,alkoxy, phenoxy or a primary or secondary amino group.

A further possibility for producing compounds of the formula I is toreact a phosphoric acid amide of the formula IX

    (Hal).sub.2 --P--A                                         (IX)

wherein "Hal" is a halogen atom, especially chlorine, and A has theabove-given meaning, with a biphenol of the formula X ##STR13## whereinR₁ and R₂ have the meanings given above.

Both types of reaction can be performed in a manner known per se, forexample between -5° C. and 80° C.; or by heating, preferably to aboveabout 80° C., for example 80°-170° C. The reaction can be performedwithout, or in the presence of, an inert solvent, such as aproticsolvents, for example ligroin, toluene, xylene, hexane, cyclohexane,dimethylformamide, dimethylacetamide, sulfolane, acetonitrile, dioxane,di-n-butyl ether, 1,2-dichloroethane, dimethylsulfoxide, ethyl acetate,methyl ethyl ketone, nitrobenzene, nitromethane, tetrahydrofuran,chloroform or trichloroethylene. If X is halogen, the reaction ispreferably carried out in the presence of a base, such as sodiumcarbonate, or an amine, for example triethylamine, pyridine orN,N-dimethylaniline. It is however quite possible to perform thereaction with an excess of amine of the formula VIII, with this actingas an acid acceptor. Amine bases used in excess can simultaneously actas solvent.

The starting materials of the formulae VII, VIII, IX and X are known,or, where they are new, they can be produced by methods analogous toknown methods. The phosphonites of the formula VI can be produced forexample analogously to the method described in Chem. Ber. 89, 1121(1956).

The compounds of the formula I can be used according to the presentinvention as stabilisers for plastics and elastomers to protect thesefrom damage caused by the action of oxygen; light and heat. Examples ofplastics concerned are the polymers listed in the GermanOffenlegungsschrift No. 2,456,864 on pages 12-14.

Suitable substrates are for example:

1. Polymers which are derived from mono-unsaturated hydrocarbons, suchas polyolefins, for example low density and high density polyethylene,which can be crosslinked, polypropylene, polyisobutylene,polymethylbut-1-ene and polymethylpent-1-ene.

2. Mixtures of the homopolymers mentioned under 1, for example mixturesof polypropylene and polyethylene, of polypropylene and polybut-1-eneand of polypropylene and polyisobutylene.

3. Copolymers of the monomers on which the homopolymers mentioned under1 are based, such as ethylene/propylene copolymers, propylene/but-1-enecopolymers, propylene/isobutylene copolymers and ethylene/but-1-enecopolymers, and also terpolymers of ethylene and propylene with a diene,for example hexadiene, di-cyclopentadiene or ethylidenenorbornene.

4. Polystyrene and its copolymers, such as SAN, ABS, IPS, ASA, andEP-modified styrene copolymers.

5. Polyamides.

6. Linear polyesters.

7. Polyurethanes.

8. Polycarbonates.

9. Elastomers, such as polybutadiene, SBR, polyisoprene, polychloropreneand nitrile rubber.

10. Thermoplastic elastomers, such as SBS, SIS and S-EP-S.

11. Polyvinyl chloride, and the like.

12. Lubricating oils having a synthetic or mineral base.

The present invention relates also to a process for stabilising polymersagainst thermooxidative degradation during production, isolation,processing and use, which process comprises incorporating into thepolymer at least one compound of the formula I.

The compounds of the formula I are incorporated into the substrates at aconcentration of 0.005 to 5 percent by weight, calculated relative tothe material to be stabilised.

Preferably 0.01 to 1.0 percent by weight, and particularly preferably0.02 to 0.5 percent by weight, of the compounds, relative to thematerial to be stabilised, is incorporated into this material.Incorporation is effected for example by mixing at least one of thecompounds of the formula I, and optionally further additives, by methodscustomary in the art, into the polymer either before or during shaping,or alternatively by application of the dissolved or dispersed compoundsto the polymers, optionally with subsequent removal of the solvent byevaporation.

The new compounds can also be added in the form of a masterbatch, whichcontains these compounds for example at a concentration of 2.5 to 25percent by weight, to the plastics to be stabilised.

In the case of crosslinked polyethylene, the compounds are added beforecrosslinking.

The invention relates therefore also to the plastics which arestabilised by the addition of 0.01 to 5 percent by weight of a compoundof the formula I, and which can optionally contain further additives.The plastics stabilised in this manner can be used in the widest varietyof forms, for example as films, fibres, tapes or profiles, or as bindersfor lacquers, adhesives or putties.

Examples of further additives which can be used together with thestabilisers according to the invention are: antioxidants, UV absorbersand light stabilisers, such as 2-(2'-hydroxyphenyl)-benzotriazoles,2,4-bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines, 2-hydroxybenzophenones,1,3-bis-(2'-hydroxybenzoyl)-benzenes, esters of substituted orunsubstituted benzoic acids and acrylates, and also nickel compounds,sterically hindered amines, oxalic acid diamides, metal deactivators,phosphites, compounds which destroy peroxide, polyamide stabilisers,basic Co stabilisers, nucleating agents or other additives, for exampleplasticisers, lubricants, emulsifiers, fillers, carbon black, asbestos,kaolin, talc, glass fibres, pigments, optical brighteners, flameproofingagents and antistatic agents.

The invention is further illustrated by the following Examples.

EXAMPLE 1

(a) A solution of 49.3 ml of piperidine (0.5 mol), 70 ml oftriethylamine and 100 ml of toluene is added dropwise to a mixture of217.5 ml of phosphorus trichloride (2.5 mols) and 200 ml of toluene. Themixture is stirred for one hour at 0°-5° C., and is then held for 10hours at the reflux temperature. After the reaction has finished, thehydrochloride is removed by filtration, and the residue is subjected tovacuum distillation. The phosphoric acid piperidide chloride boils at55° C./0.4 mm Hg.

(b) 9.3 g (0.05 mol) of phosphorus acid piperidide dichloride and 20.5 g(0.05 mol) of 4,4',6,6'-tetra-tert-butyl-2,2'-biphenol in 50 ml oftriethylamine are refluxed for 20 hours. The hydrochloride is separatedand the unreacted triethylamine is removed to leaveN-(2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6-yl)-piperidineas an amorphous residue.

Elementary analysis--Calculated: C, 75.68%; H, 9.62%; N, 2.6%; P, 5.9%.Found: C, 76.2%; H, 9.5%; N, 2.6%; P, 5.8%.

EXAMPLE 2

170 g (0.414 mol) of 4,4',6,6'-tetra-tert-butyl-2,2'-biphenol in 150 mlof toluene is heated to 80°-90° C. in a nitrogen atmosphere, and 40 ml(0.458 mol) of phosphorus trichloride is added dropwise in the course of2 hours. The reaction mixture is stirred at reflux temperature for 4hours and, towards the end of the reaction, nitrogen gas is againintroduced. There is then added dropwise at reflux temperature, during11/2 hours, a solution of 53.5 g (0.414 mol) of dibutylamine and 41.9 g(0.414 mol) of triethylamine in 80 ml of toluene. After 15 hours, thereaction mixture is allowed to cool to room temperature, and thetriethylamine hydrochloride which has precipitated is filtered off. Thetoluene is afterwards evaporated off, and theN-(2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,3,2]dioxaphosphepin-6-yl)-dibutylamineobtained has a melting point of 140° C.

EXAMPLES 3-10

170 g (0.414 mol) of 4,4',6,6'-tetra-tert-butyl-2,2'-bisphenol and 36.1ml of phosphorus trichloride in 150 ml of xylene are heated to 110°-115°C. After 4 hours, there is added dropwise to the reaction mixture, inthe course of 1.5 hours, a solution of 36.1 g (0.414 mol) of morpholineand 58 ml of triethylamine in 80 ml of xylene, and stirring ismaintained for a further 20 hours at 110°-120° C. The triethylaminohydrochloride is then filtered off, and the solvent is filtered off invacuo to leave the product,N-(2,4,8,10-tetra-tert-butyl-dibenz[d,f][1,2,3]dioxaphosphepin-6-yl)-morpholine,as a crystalline residue (m.p. 140°-143° C.).

The following products are obtained by a procedure analogous to thatdescribed in Example 3.

    ______________________________________                                        No.  Formula            Melting Point                                         ______________________________________                                        4    N--(2,4,8,10-tetra-tert-butyl-                                                                   189° C.                                             dibenz[d,f][1,3,2]dioxa-                                                      phosphepin-6-yl)-diiso-                                                       propylamine                                                              5    N--(2,4,8,10-tert-butyl-                                                                         270° C.                                             dibenz[d,f][1,3,2]dioxa-                                                      phosphepin-6-yl)-dicyclo-                                                     hexylamine                                                               6    N--(4,8-di-tert-butyl-2,10-                                                                      131-134° C.                                         di-tert-octyl-dibenz[d,f]-                                                    [1,3,2]dioxaphosphepin-6-                                                     yl)-morpholine                                                           7    N,N'--di-(2,4,8,10-tetra-                                                                        260° C.                                             tert-butyl-dibenz[d,f][1,3,                                                   2]dioxaphosphepin-6-yl)-                                                      piperazine                                                               8    N--(2,4,8,10-tetra-tert-butyl-                                                                   Characteristics                                            dibenz[d,f][1,3,2]dioxa-                                                                         oil                                                        phosphepin-6-yl)-p-dodecyl-                                                                      cal.   P 4.42%  N 2.00%                                    phenylamine        found  P 3.57%  N 1.8%                                9    N,N--di-(2,4,8,10-tetra-                                                                         260° C.                                             tert-butyl-dibenz[d,f][1,3,                                                   2]dioxaphosphepin-6-yl)-                                                      ethylenediamine                                                          10   N--(2,4,8,10-tetra-tert-octyl-                                                                   oil                                                        dibenz[d,f][1,3,2]dioxa-                                                      phophepin-6-yl)-dibutyl-                                                      amine                                                                    ______________________________________                                    

EXAMPLE 11

100 parts of high-density polyethylene having a molecular weight ofabout 500,000 ("Lupolen 5260 Z" in powder form, BASF) containing 0.05part ofpentaerithritol-tetra-[3,5-di-tert-butyl-(4-hydroxyphenyl)-propionate]are mixed dry with 0.1 part of each of the phosphonites shown in Table 1below. The mixtures are kneaded in a Brabender plastograph at 220° C. at50 r.p.m. During this time, the kneading resistance is continuouslyrecorded as a turning moment. As a result of crosslinking of thepolymer, there occurs in the course of kneading a rapid increase in theturning moment after an initial period of constant value. Theeffectiveness of the stabilisers is manifested by a lengthening of thetime in which this value remains constant.

                  TABLE 1                                                         ______________________________________                                        Parts of        Time in minutes unil the                                      phosphonite     turning moment changes                                        ______________________________________                                        none            3                                                             0.1 part of compound 1                                                                        17.5                                                          0.1 part of compound 4                                                                        13.5                                                          0.1 part of compound 5                                                                        9.5                                                           ______________________________________                                    

What is claimed is:
 1. A composition which comprises(a) a polymericorganic material to be stabilized, and (b) 0.005 to 5 percent by weight,based on component (a), of a compound of formula I ##STR14## wherein R₁and R₂ are each α-branched C₃ -C₈ alkyl,A is a group --N(R₃)R₄ (III),wherein R₃ is hydrogen, C₁ -C₂₂ alkyl, C₂ -C₂₁ oxa- or thiaalkyl, C₃-C₁₈ alkenyl, C₃ -C₁₈ alkynyl, C₂ -C₆ hydroxyalkyl, C₃ -C₂₄alkoxycarbonylalkyl, C₅ -C₁₂ cycloalkyl, C₆ -C₁₄ aryl, C₇ -C₁₅ alkaryl,C₇ -C₁₅ aralkyl, a C₅ -C₁₇ piperidin-4-yl group or said groupsubstituted by up to five methyl or ethyl groups; or a group of theformula II ##STR15## in which R₁ and R₂ have the meanings given above,R₄ is C₁ -C₂₂ alkyl, C₂ -C₂₁ oxa- or thiaalkyl, C₃ -C₁₈ alkenyl, C₃ -C₁₈alkynyl, C₂ -C₆ hydroxyalkyl, C₃ -C₂₄ alkoxycarbonylalkyl, C₅ -C₁₂cycloalkyl, C₆ -C₁₄ aryl, C₇ -C₁₅ alkaryl, C₇ -C₁₅ aralkyl, a C₅ -C₁₇piperidin-4-yl group or said group substituted by up to five methyl orethyl groups; a group of the formula IV ##STR16## wherein R₃ has themeaning given above,n is 0 or 1, R₅ is C₂ -C₂₂ alkylene; C₄ -C₂₂alkenylene, C₄ -C₂₂ alkynylene or C₅ -C₉ cycloalkylene, each of whichcan be interrupted with one or two oxygen or sulfur atoms, or R₅ is agroup of the formula VI ##STR17## in which R₆ is --O--, --S-- or--(R₇)C(R₈)--, wherein R₇ and R₈ independently of one another arehydrogen or C₁ -C₈ alkyl, or R₇ and R₈ together with the C atom to whichthey are attached form C₅ -C₁₂ cycloalkyl, or R₇ and R₈ together are1,4-cyclohexylenedimethylene or 1,3,3-trimethylcyclohexylene-1,5, or R₅is also phenylene, biphenylene or a group of the formula ##STR18##wherein R₆ has the meaning given above, and r, t and n independently ofone another are 2, 3, 4, 5 or 6, m is 0, 1, 2 or 3, Q is a group of theformula II, wherein R₁ and R₂ have the meanings given above, or R₃ andR₄ together with the N atom to which they are attached form apyrrolidine, oxazolidine, piperidine or morpholine ring; or saidpyrrolidine, said oxazolidine, said piperidine or said morpholinesubstituted by up to five methyl or ethyl groups; or R₃ and R₄ togetherform the radical --CH₂ --CH₂ --N(Q)--CH₂ --CH₂ -- wherein Q has themeaning given above.
 2. A composition according to claim 1 where in thecompound of formula IR₁ and R₂ are each α-branched C₃ -C₈ alkyl, A is agroup --N(R₃)R₄ (III), wherein R₃ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₄alkenyl, C₃ -C₄ alkynyl, C₃ -C₂₄ alkoxycarbonylmethyl or -ethyl, C₅ -C₁₂cycloalkyl, phenyl, benzyl, C₇ -C₁₅ alkaryl; a C₅ -C₁₇ piperidin-4-ylgroup or said group substituted by up to five methyl or ethyl groups; ora group of the formula II, wherein R₁ and R₂ have the meaning givenabove, R₄ is C₁ -C₁₈ alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, C₃ -C₂₄alkoxycarbonylmethyl or -ethyl, C₅ -C₁₂ cycloalkyl, phenyl, benzyl, C₇-C₁₅ alkaryl; a C₅ -C₁₇ piperidin-4-yl group or said group substitutedby up to five methyl or ethyl groups; a group of the formula IV or V,wherein R₃ has the meaning given above, n is 0 or 1, R₅ is C₂ -C₉alkylene which can be interrupted with one or two oxygen or sulfuratoms, or it is cyclohexylene, or a group of the formula VI, wherein R₆is --O--, --S-- or --(R₇)C(R₈)--, wherein R₇ and R₈ independently of oneanother are hydrogen or methyl, or R₇ and R₈ together with the C atom towhich they are attached form cyclohexylene, or R₇ and R₈ together are1,4-cyclohexylenedimethylene or 1,3,3-trimethyl-cyclohexylene-1,5, r, tand n are 2 or 3, m is 0 or 1, Q is a group of the formula II, whereinR₁ and R₂ have the meanings given above, or R₃ and R₄ together with theN atom to which they are attached form a pyrrolidine, oxazolidine,piperidine or morpholine ring, or R₃ and R₄ together are the radical--CH₂ CH₂ --N(Q)--CH₂ CH₂ -- wherein Q has the meaning given above.
 3. Acomposition according to claim 1 where in the compound of formula IR₁and R₂ are each α-branched C₃ -C₈ alkyl, A is a group --N(R₃)R₄ (III)wherein R₃ is hydrogen, C₁ -C₁₈ alkyl, allyl, propargyl, C₃ -C₁₄alkoxycarbonylmethyl, C₃ -C₁₅ alkoxycarbonylethyl or C₅ -C₈ cycloalkyl,R₄ is C₁ -C₄ alkyl, allyl, propargyl, C₃ -C₁₄ alkoxycarbonylmethyl, C₃-C₁₅ alkoxycarbonylethyl, C₅ -C₈ cycloalkyl, or a group of the formulaIV or V, wherein R₃ has the meaning given above, n is 1, R₅ is C₂ -C₆alkylene, r, t and n are 2 or 3, m is 0, Q is a group of the formula II,wherein R₁ and R₂ have the meanings given above, or R₃ and R₄ togetherwith the N atom to which they are attached form a piperidine ormorpholine ring, or R₃ and R₄ together are the radical --CH₂ CH₂--N(Q)--CH₂ CH₂ -- wherein Q has the meaning given above.
 4. Acomposition according to claim 1 where in the compound of formula IR₁and R₂ are α-branched C₃ -C₈ alkyl, A is a group --N(R₃)R₄ (III),wherein R₃ is hydrogen, C₁ -C₁₂ alkyl or cyclohexyl, R₄ is C₁ -C₄ alkyl,cyclohexyl, or a group of the formula IV, wherein R₃ has the meaninggiven above, and Q is a group of the formula II, wherein R₁ and R₂ havethe meanings given above, n is 1, R₅ is C₂ -C₆ alkylene, or R₃ and R₄together with the N atom to which they are attached form a piperidine ormorpholine ring, or R₃ and R₄ together are the radical --CH₂ CH₂--N(Q)--CH₂ CH₂ -- wherein Q has the meaning given above.
 5. Acomposition according to claim 1 where in the compound of formula I R₁and R₂ are tert-butyl or tert-octyl.
 6. A composition according to claim1 where in the compound of formula I, A is --N(R₃)R₄ in which R₃ is apiperidin-4-yl group of the formula XI ##STR19## wherein R₉ is hydrogenor methyl, and R₁₀ is hydrogen, oxyl, C₁ -C₁₈ alkenyl, C₃ -C₆ alkynyl,C₇ -C₁₂ aralkyl, C₂ -C₂₁ alkoxyalkyl, an aliphatic acyl group having 1-4C atoms, or a group --CH₂ COOR₁₁, in which R₁₁ is C₁ -C₁₂ alkyl, C₃ -C₈alkenyl, phenyl, C₇ -C₈ aralkyl or cyclohexyl.
 7. A compositionaccording to claim 6 where in the compound of formula I both R₃ and R₄are each a group of formula XI.
 8. A composition according to claim 6where in the compound of formula I R₉ is hydrogen, and R₁₀ is hydrogen,C₁ -C₈ alkyl, allyl, benzyl or acetyl.
 9. A composition according toclaim 7 where in the compound of formula I R₉ is hydrogen, and R₁₀ ishydrogen, C₁ -C₈ alkyl, allyl, benzyl or acetyl.
 10. A compositionaccording to claim 8 wherein R₁₀ is hydrogen, methyl or acetyl.
 11. Acomposition according to claim 9 wherein R₁₀ is hydrogen, methyl oracetyl.
 12. A composition according to claim 1 wherein the compound offormula I isN-(2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepin-6-yl)-dibutylamine.13. A composition according to claim 1 wherein component (a) is apolyolefin.
 14. A composition which comprises(a) a polymeric organicmaterial to be stabilized, and (b) 0.005 to 5 percent by weight, basedon component (a), of a compound of formula I ##STR20## wherein R₁ and R₂are each α-branched C₃ -C₈ alkyl,A is a group --N(R₃)R₄ (III), whereinR₃ and R₄ together with the N atom to which they are attached form apyrrolidine, oxazolidine, piperidine or morpholine ring; or saidpyrrolidine, said oxazolidine, said piperidine or said morpholine ringsubstituted by up to five methyl or ethyl groups; or R₃ and R₄ togetherform the radical --CH₂ --CH₂ --N(Q)--CH₂ --CH₂ -- wherein Q is a groupof the formula II ##STR21## where R₁ and R₂ have the meanings givenabove.
 15. A composition according to claim 14 where in the compound offormula IR₁ and R₂ are each α-branched C₃ -C₈ alkyl, A is a group--N(R₃)R₄ (III), R₃ and R₄ together with the N atom to which they areattached form a pyrrolidine, oxozolidine, piperidine or morpholine ring,or R₃ and R₄ together are the radical --CH₂ --CH₂ --N(Q)--CH₂ --CH₂ --wherein Q is a group of formula II wherein R₁ and R₂ have the meaningsgiven above.
 16. A composition according to claim 14 where in thecompound of formula IR₁ and R₂ are each α-branched C₃ -C₈ alkyl, A is agroup --N(R₃)R₄ (III) wherein R₃ and R₄ together with the N atom towhich they are attached form a piperidine or morpholine ring, or R₃ andR₄ together are the radical --CH₂ --CH₂ --N(Q)--CH₂ --CH₂ -- wherein Qis a group of formula II wherein R₁ and R₂ have the meanings givenabove.
 17. A composition according to claim 14 where in the compound offormula IR₁ and R₂ are α-branched C₃ -C₈ alkyl, A is a group --N(R₃)R₄(III), wherein R₃ and R₄ together with the N atom to which they areattached form a piperidine or morpholine ring, or R₃ and R₄ together arethe radical --CH₂ --CH₂ --N(Q)--CH₂ --CH₂ -- wherein Q is a group offormula II wherein R₁ and R₂ have the meanings given above.
 18. Acomposition according to claim 14 where in the compound of formula I R₁and R₂ are tert-butyl or tert-octyl.
 19. A composition according toclaim 14 where in the compound of formula I R₃ and R₄ together with theN atom to which they are attached form a pyrrolidine, piperidine ormorpholine ring; or said pyrrolidine, said piperidine or said morpholinering substituted by up to five methyl or ethyl groups.
 20. A compositionaccording to claim 19 where in the compound of formula I R₃ and R₄together with the N atom to which they are attached form a pyrrolidine,piperidine or morpholine ring.
 21. A composition according to claim 14where the compound of formula I isN-(2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxa-phosphepin-6-yl)-piperidine.
 22. A composition according to claim 14wherein component (a) is polyolefin.